Oxidative stability of palm‐ and soybean‐based medium‐ and long‐chain triacylglycerol (MLCT) oil blends

BACKGROUND: Medium‐ and long‐chain triacylglyerols (MLCT) enzymatically esterified using Lipozyme RM IM lipase has very low oxidative stability as it does not contain any antioxidants. The aim of this work was to study the ability of various antioxidants to increase the oxidative stability of palm‐ and soybean‐based MLCT blends which assist to bring up the oxidative stability of both MLCT blends. In this study, the effectiveness of rosemary extracts, sage extracts, tert‐butylhydroquinone (TBHQ) and mixtures of tert‐butyl‐4‐hydroxyanisole (BHA) and tert‐butyl‐p‐hydroxytoluene (BHT) in protecting against oxidation of various MLCT blends was investigated. RESULTS: Blending of MLCT oil with either palm olein or soybean oil improved its smoke point values and oxidative stability. TBHQ addition to both palm‐ and soybean‐based MLCT blends increased oxidative stability. Combination of BHA and BHT showed no significant improvement (P > 0.05) in ability to protect blends from oxidation compared to natural antioxidants such as sage or rosemary extracts. CONCLUSION: Blended oils with 500 g kg^?1 MLCT and 500 g kg^?1 palm olein (MP5) were the most suitable for use at high temperature based on the fatty acid composition of the MLCT blends, which subsequently had an effect on thermal oxidative stability. In general, addition of either natural or synthetic antioxidant assisted in improving the antioxidative strength of both MLCT blends. MLCT blends with added TBHQ showed the highest thermal oxidative stability among the antioxidants used. Copyright © 2008 Society of Chemical Industry     

Addition of synthetic and natural antioxidants to α-tocopheryl acetate supplemented beef patties: effects of antioxidants and packaging on lipid oxidation

Friesian steers (n=5), aged 26–27 months, were fed a diet containing 2000 (supplemented) IU α-tocopheryl acetate/head/day for approximately 50 days prior to slaughter. Muscularis semimembranosus muscles from supplemented cattle were held in frozen storage (−20°C×12 weeks) following which they were minced and divided into five batches. The batches contained: (1) control, containing only vitamin E supplemented beef (C); (2) vitamin E supplemented beef with 4% soya oil (S); (3) vitamin E supplemented beef mixed with 0.2% Duralox NMC dissolved in 4% soya oil (R1); (4) vitamin E supplemented beef mixed with 0.25% Herbalox type 25 (containing 25 natural antioxidant extracts of rosemary) dissolved in 4% soya oil (R2); and (5) vitamin E supplemented beef mixed with a 1:1 mixture of 0.01% (w/w) BHA and 0.01% (w/w) BHT dissolved in 4% soya oil (B). The meat was then aerobically packaged (A) or packaged under the following modified atmospheres (MAP); 30:70 (M₁); 70:30 (M₂) or 80:20 (M₃) (O₂:CO₂). Oxidative stability (TBARS) and Hunter ‘a’ values (redness) were determined in all beef patties over 8 days of refrigerated (4°C) storage. Under MAP or aerobic packaging conditions, elevated oxygen levels brought about increased (P<0.05) TBARS numbers during refrigerated storage. However, the addition of rosemary extracts or BHA/BHT significantly (P<0.05) improved the oxidative stability of dietary α-tocopheryl acetate supplemented beef. Rosemary extracts were as effective in reducing TBARS as the combination of synthetic antioxidants, BHA/BHT.     

Antioxidant activity of hydroxytyrosol in frankfurters enriched with n-3 polyunsaturated fatty acids

The capacity of hydroxytyrosol (HXT) to inhibit lipid oxidation in cooked pork meat batter, oil-in-water emulsions and potential functional frankfurters formulated with a healthier oil combination (as animal fat replacer) was studied during chilling storage, and its effect compared with those produced by synthetic antioxidants (BHA/BHT). Although efficiency varied, HXT was an effective antioxidant during chilling storage in the three food matrices studied. In general the order of inhibition capacity of HXT against lipid oxidation (thiobarbituric acid-reactive substances-TBARS) was cooked meat batter > oil-in-water emulsion > frankfurters, whereas in the case of BHA/BHT (with lower inhibitory activity than HXT) it was cooked meat batter > oil-in-water emulsion, and there was no antioxidative effect in frankfurters. Whereas significant correlations were established between lipid oxidation (TBARS) and antioxidative capacity measured by photochemiluminescence (PCL) in frankfurters supplemented with HXT and BHA/BHT, no significant correlations were found between ferric reducing/antioxidant power assay (FRAP) and TBARS and PCL.     

Natural antioxidants protecting irradiated beef burgers from lipid oxidation

The effect of butylated hydroxytoluene/butylated hydroxyanisole blend (BHT/BHA), and rosemary and oregano extracts, added individually or in combination, on lipid oxidation and fatty acid composition was investigated on irradiated frozen beef burgers. Irradiation treatment was carried out using a ⁶⁰CO semi-industrial irradiator at doses of 6, 7 and 8 kGy, and then the treated meat samples were stored at −20 °C for 90 days. Lipid oxidation and fatty acid composition of beef samples were evaluated by measurement of TBARS and gas chromatography, respectively. The results of the experiment showed that rosemary extract, applied alone and in combination with either BHT/BHA or oregano extract, was more effective in maintaining a low oxidation level in the samples compared to oregano extract used individually or in combination with BHT/BHA. Results also showed no significant differences (p > 0.05) in fatty acid composition in all analyzed samples, although some changes in terms of decreased PUFA and MUFA, beside of slight increase of SFA content were observed. However, these differences do not correlate positively neither with the irradiation dose nor the type of antioxidant. Thus, there is a potential application of these spices as natural antioxidants in irradiated meats.     

Antioxidant and pro-oxidant activity of green tea extracts in marine oils

The activity of green tea extracts (GTE) on the oxidation of refined, bleached and deodorized (RBD) seal blubber oil (SBO) and menhaden oil (MHO) was examined under Schaal oven conditions at 65 °C. Progression of oxidation was monitored using weight gain, peroxide value (PV) and 2-thiobarbituric acid-reactive substances (TBARS) data. GTE exhibited a pro-oxidant effect in both oils examined, perhaps due to the catalytic effect of their chlorophyll constituents. Therefore, in follow-up experiments, a column chromatographic technique was employed to remove chlorophyll from GTE. The resultant dechlorophyllized green tea extract (DGTE) was applied to both SBO and MHO at 100, 200, 500 and 1000 ppm levels. The antioxidant activity of DGTE was compared with the effects of the commonly-used antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ) at 200 ppm and α-tocopherol at 500 ppm. DGTE at ≥200 ppm exhibited excellent antioxidant activity in both oils and its efficacy was higher than that of BHA, BHT and α-tocopherol, but less than that of TBHQ.     

STABILIZATION OF MARINE OILS WITH FLAVONOIDS

Antioxidant activity of a number of flavonoids in refined-bleached and deodorized (RBD) seal blubber oil (SBO) and menhaden oil (MHO) was compared with that of commercially used antioxidants, namely butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ) as well as α-tocopherol. The study was carried under Schaal oven conditions at 65C and progression of oxidation was followed by monitoring weight gain, peroxide value (PV) and 2-thiobarbituric acid reactive substances (TBARS) value. Among the flavonoids tested in this study, the flavonols, namely myricetin, quercetin and morin exhibited a stronger antioxidant activity than BHA and BHT and effectively stabilized both SBO and MHO. Myricetin was the most effective flavonoid tested in this study and its effect in reducing lipid oxidation was similar to that of TBHQ.     

质量控制天然维生素E对食用油氧化稳定性的影响

本文以食用菜籽油为对象,研究了天然维生素Ｅ对植物油脂氧化稳定性的影响。结果表明：天然维生素Ｅ比叔丁基羟基茴香醚（ＢＨＡ）和二叔丁基羟基甲苯（ＢＨＴ）更适合于添加至食用油脂中作为抗氧化剂;在０～９５ｍｇ／Ｌ之间,随着天维生素Ｅ添加量的增加,食用油脂的氧化稳定性指数（ＯＳＩ）值也增高,其抗氧化效果愈好。     

The antioxidative properties of rosemary oleoresin and inhibition of off-flavours in precooked roast beef slices

The antioxidant properties of rosemary oleoresin in precooked roast beef slices were compared to those of a butylated hydroxyanisole/butylated hydroxytoluene (BHA/BHT) combination, sodium tripolyphosphate and sodium citrate, during both refrigerated and frozen storage. Their antioxidant properties were measured by means of TBARS (TBA-reactive substances) and sensory scores. Sodium tripolyphosphate was the most effective antioxidant during both storage periods. Rosemary oleoresin in combination with sodium tripolyphosphate proved to be effective during both storage periods, but in particular, during frozen storage at preventing an increase in TBARS and at improving the flavour preference for the roast beef slices. Sodium citrate proved to be an ineffective antioxidant. The treatments containing salt, phosphate plus BHA/BHT and salt plus BHA/BHT had comparable antioxidative properties to the treatments containing salt, phosphate and rosemary and salt and rosemary, respectively. No overall significant correlation coefficients were obtained between the TBARS and the sensory scores. © 1998 SCI.     

Synergistic antioxidant and antibacterial activity of rosemary plus butylated derivatives

Antioxidant and antibacterial activity of a methanol rosemary extract (RE) containing 30% carnosic acid (CA), 16% carnosol (COH) and 5% rosmarinic acid (RA) was studied in vitro alone and in combination with the antioxidant food additives butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). The antioxidant efficiency of the extract, CA, and RA, was determined by a kinetic analysis of the 2,2-diphenyl-2-picrylhydrazyl hydrate radical (DPPH·) scavenging activity. RE showed two different rate slopes in the reduction of DPPH· vs. time curve, which correlated with the distinct behaviours of RA and CA; pure RA reached the plateau more rapidly than CA. A synergistic antioxidant effect between RE and BHT was demonstrated by isobolographic analysis and a synergistic interaction of RE with BHA to inhibit Escherichia coli and Staphylococcus aureus growth was observed. Therefore, rosemary not only enhances the antioxidant efficiency of BHA and BHT, but also the antibacterial effect of BHA; allowing a decrease from 4.4 to17 folds in the amounts of the synthetic compounds used.     

Antioxidant activity of natural plant sources in dairy dessert (Sandesh) under thermal treatment

Natural sources of antioxidant viz. beet (Beta vulgaris), mint (Mentha spicata L.) and ginger (Zingiber officinale L.) have been used to fortify sandesh (a heat desiccated product of coagulated milk protein mass called chhana which is in turn a heat and acid coagulated product of milk, analogous to cottage cheese). Three sets of experiments viz. antioxidant activity, peroxide value and ultra-violet absorbance were done to evaluate the effectiveness of natural antioxidants in reducing lipid oxidation in sandesh as compared to synthetic antioxidants like tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) under thermal treatment. Among the natural sources, ginger has the highest antioxidant activity and it was similar to TBHQ and BHA-BHT combined. Results of the antioxidant activity differed from those of the oven test at 63 °C particularly for ginger and BHA-BHT combined. Control sandesh (without any antioxidants) showed the highest peroxide value and ultra-violet absorption. All the natural sources and their combinations significantly improved the oxidative stability of sandesh and their effectiveness was comparable with synthetic antioxidant TBHQ, a combination of BHA and BHT. Among the natural sources, although ginger had the highest antioxidant activity but mint showed better effectiveness in the inhibition of lipid oxidation. Regarding antioxidant activity and lipid oxidation, combination of mint or ginger with beet showed better result as compared to beet alone. Besides, sensory evaluation of freshly prepared natural source fortified sandesh samples was done as compared to control sandesh in order to commercialize the herbal sandesh in market. Sandesh containing beet, ginger, combination of beet with ginger or mint, or combination of mint with ginger were more acceptable to panelist than control sandesh.     

Antioxidative Activities of Ginkgo biloba Extract on Oil/Water Emulsion System Prepared from an Enzymatically Modified Lipid Containing Alpha‐Linolenic Acid

Abstract: The desired mix of alpha‐linolenic acid (ALA)‐enriched structured lipid (SL) and physically blended lipid (PB) was prepared from grape seed oil and perilla oil at a weight ratio of 3:1. The major triacylglycerol species (LnLnL) in PB was drastically increased after interesterification (SL), from 0.5% to 16.8%. After the reaction, the total unsaturated fatty acid at the sn‐2 position was decreased from 98.83% in PB to 91.36% in SL. The reduction of vitamin E compounds was also observed. Compared with a PB‐based emulsion, SL‐based emulsions showed oxidative instability, as assessed by lipid hydroperoxide (LOOH) and 2‐thiobarbituric acid‐reactive substances (TBARS) values, which was mainly due to the SL which contained less LA, ALA, and ΣUSFA at the sn‐2 position and less γ‐tocopherol than did PB. PB‐, and SL‐based emulsions with Ginkgo biloba extract (GBE) which showed significantly lower values of LOOH and TBARS compared to a blank control. GBE was effective in retarding the oxidation of the emulsion by quenching the free radicals in the water phase of the emulsion and inhibiting the formation of primary and secondary oxidation products. These results indicate that GBE could be used as an antioxidant additive for stabilizing ALA‐enriched emulsions. Practical Application: The results suggest the possibility to supplement Ginkgo biloba extract in alpha linolenic acid‐enriched structured lipid‐based emulsions which would increase the therapeutic value and enhance the antioxidant potential of the emulsions.     

复配天然抗氧化剂对食用油脂抗氧化效果研究

对天然抗氧化剂复配配方对食用油的抗氧化能力进行研究。根据正交试验结果,各种天然抗氧化剂在组分中的主次因素为迷迭香提取物＞甘草提取物＞茶多酚＞ VE,优化得出复合天然抗氧化剂的复配组合为迷迭香0.08%、茶多酚0.06%、甘草提取物0.08%、VE0.01%。此优化的配方对食用油的抗氧化能力弱于TBHQ,但强于BHA 和BHT。     

Inhibition of Lipid Oxidation and Rancidity in Precooked Pork Patties by Radical‐Scavenging Licorice (Glycyrrhiza glabra) Extract

This study investigated the efficacy of licorice extract (LE) to curtail lipid oxidation and protect sensory attributes of ground pork during refrigerated and frozen storage. Pork patties (20% fat) were formulated with 0%, 0.02%, 0.05%, and 0.1% (meat basis) LE or rosemary extract (RE) as comparison or 0.01% (fat basis) BHA with 0 or 1.5% NaCl. Raw and precooked (75 °C) patties were packaged in polyvinylchloride overwrapped trays and stored at 2 °C up to 7 and 14 d, respectively, or at –20 °C up to 6 mo. Lipid oxidation (thiobarbituric acid‐reactive substances [TBARS]) and sensory attributes of stored patty samples were evaluated, radical scavenging activity of the LE was measured, and the active phenolic compounds were identified. Cooking yield (<85%) was similar among antioxidant treatments, and lipid oxidation was minimal in refrigerated or frozen raw samples. However, TBARS values in refrigerated precooked control patties (0.22 mg/kg) rose to 9.3 to 9.4 mg/kg after 14 d, compared to 3.4 to 4.4 and 4.4 to 6.9 mg/kg in patties treated with 0.1% LE and RE, respectively. In frozen precooked samples, TBARS (0.22 mg/kg) increased to 1.3 mg/kg (P < 0.05) in control patties after 6 mo and had no significant change in patties treated with 0.1% LE or 0.01% butylated hydroxyanisol. Sensory panel evaluation confirmed strong inhibition of rancidity production by LE, corroborating its remarkable antiradical activity due to the presence of multiple phenolics. The results indicate that licorice has great potential as a natural antioxidative additive to extend the shelf‐life of precooked pork.     

Beneficial effect of the unsaponifiable matter from rice bran on oxidative stress in vitro compared with α‐tocopherol

Unsaponifiable matter (UM) was prepared from rice bran using n‐hexane extraction followed by removal of its fatty acid methyl ester with supercritical CO₂ under heat‐stable conditions. The UM was made up of 1% of vitamin E isomers, 28% of γ‐oryzanol and 71% of uncharacterized compounds. The aim of this study was to determine the antioxidant activities of the UM, using α‐tocopherol (α‐T) as a positive control, by measuring the Fe³⁺‐reducing antioxidant power (FRAP), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH^?) free‐radical‐scavenging property and lipid peroxidation in rat liver microsomes. In addition, the effects of the UM on the tert‐butyl hydroperoxide (t‐BOOH)‐induced cytotoxicity in cultured rat hepatocytes were also investigated. In FRAP assay and DPPH^? free‐radical‐scavenging assay, the results were expressed g^?1α‐T or g^?1 UM. The amount of UM used in lipid peroxidation assay and cytotoxicity assay was the amount required to have equal amounts of total vitamin E isomers in the sample and the control α‐T. The UM, as well as α‐T, exhibited significant antioxidant activities in FRAP, radical‐scavenging and membrane‐lipid oxidation. The FRAP value for total vitamin E isomers in the UM (TVEIUM) was 9.1 times higher than that for α‐T. In terms of their capacities to perform radical‐scavenging and lipid peroxidation, both TVEIUM and α‐T showed similar antioxidant activities. In experiments using cultured rat hepatocytes, the t‐BOOH‐induced lactate dehydrogenase release was significantly inhibited by the addition of 63.5 and 160 µg ml^?1 of TVEIUM treatments (84 and 89%, respectively), and that of 63.5 and 160 µg ml^?1 of α‐T treatment (88 and 93%, respectively). The antioxidant function against oxidative stress of the UM prepared from rice bran may extend its use to being a potential dietary supplement. Copyright © 2004 Society of Chemical Industry     

气相色谱法测定食用油中BHA和BHT残留量的对比研究

目的建立气相色谱法测定食用油中叔丁基羟基茴香醚(butyl hydroxyanisole,BHA)和二丁基羟基甲苯(butylated hydroxytoluene,BHT)的残留量。方法使用无水乙醇萃取样品,经中性氧化铝吸附杂质,HP-5毛细管柱分离,使用气相色谱仪定量分析BHA和BHT在食用油中的残留量。同时,与GB/T 5009.30中的方法进行对比,考察了本方法的线性、重现性、回收率和精密度。结果本方法中BHA和BHT的线性范围分别为2.02~40.48 ng和2.07~41.36 ng,标准曲线方程分别为Y=16.61X+10.03(r=0.9996)和Y=20.14X+16.56(r=0.9997);BHA和BHT的检出限分别为92.4 ng/kg和108.6 ng/kg,加标回收率分别为98.94%(相对标准偏差为0.33%)、98.69%(相对标准偏差为0.34%)。结论本实验建立的方法灵敏度高、定量准确,和国标法相比,具有简单实用的特点,适合食用油中BHA和BHT残留量的检测。     

Comparison of a natural rosemary extract and BHA/BHT for relative antioxidant effectiveness in pork sausage

A commercial rosemary extract was evaluated for antioxidant effectiveness at concentrations of 1500 and 2500 ppm in frozen and precooked-frozen pork sausage, and from 500 to 3000 ppm in refrigerated, fresh pork sausage. Thiobarbituric acid-reactive substances (TBARS), objective color values and sensory panel scores, were assessed. For refrigerated sausage, the rosemary extract at 2500 ppm was equally effective as butylated hydroxy anisole (BHA)/butylated hydroxy toluene (BHT). Similarly, the rosemary extract was equally effective as BHA/BHT in maintaining low TBARS values of precooked-frozen sausage. However, the rosemary extract was more effective than BHA/BHT for preventing increased TBARS values or loss of red color in raw frozen sausage.     

Effectiveness of antioxidant‐impregnated film in retarding lipid oxidation

The effectiveness of an antioxidant‐impregnated film to retard autoxidation of a packaged model product containing linoleic acid, via an evaporation/sorption mechanism, was evaluated as a function of storage time and temperature. The rate of loss of antioxidant from the package film structure was described by a first‐order expression. The first‐order rate constants were dependent on the initial concentration of antioxidant in the film. The rate of loss of 3,5‐di‐tert‐butyl‐4‐hydroxytoluene (BHT) from the package film structure was found to be much higher than the rate of loss of α‐tocopherol at both storage conditions (23 and 45 °C, 50% relative humidity) studied. A freeze‐dried model food product system was developed as the source for the autoxidation of linoleic acid in storage stability studies. The storage stability of this model food system packaged with antioxidant‐impregnated film pouches was evaluated. Hexanal as an index of oxidation from the model product system was collected by a dynamic purge and trap system and quantified by a gas chromatography/mass spectrometry procedure. The BHT‐impregnated laminate pouch showed a notable effectiveness in retarding lipid oxidation of the model product at 45 °C as a function of storage time. The control (non‐antioxidant) and α‐tocopherol‐impregnated laminate pouch structures showed no effect on retarding lipid oxidation of the model product during storage at 45 °C. Copyright © 2004 Society of Chemical Industry